WO1998019747A1 - Balle de golf multicouche et composition - Google Patents

Balle de golf multicouche et composition Download PDF

Info

Publication number
WO1998019747A1
WO1998019747A1 PCT/US1997/020123 US9720123W WO9819747A1 WO 1998019747 A1 WO1998019747 A1 WO 1998019747A1 US 9720123 W US9720123 W US 9720123W WO 9819747 A1 WO9819747 A1 WO 9819747A1
Authority
WO
WIPO (PCT)
Prior art keywords
core
golf ball
ball
cover
layer
Prior art date
Application number
PCT/US1997/020123
Other languages
English (en)
Inventor
Christopher Cavallaro
Murali Rajagopalan
Samuel A. Pasqua, Jr.
Herbert C. Boehm
Kevin M. Harris
Jeffrey L. Dalton
Original Assignee
Acushnet Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Acushnet Company filed Critical Acushnet Company
Priority to JP52173298A priority Critical patent/JP3607301B2/ja
Priority to GB9910473A priority patent/GB2333715B/en
Priority to AU52460/98A priority patent/AU5246098A/en
Publication of WO1998019747A1 publication Critical patent/WO1998019747A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/0023—Covers
    • A63B37/0029—Physical properties
    • A63B37/0035—Density; Specific gravity
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/0023—Covers
    • A63B37/0029—Physical properties
    • A63B37/0037—Flexural modulus; Bending stiffness
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/005—Cores
    • A63B37/006—Physical properties
    • A63B37/0064—Diameter
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/005—Cores
    • A63B37/006—Physical properties
    • A63B37/0065—Deflection or compression
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/005—Cores
    • A63B37/006—Physical properties
    • A63B37/0066—Density; Specific gravity
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/007—Characteristics of the ball as a whole
    • A63B37/0072—Characteristics of the ball as a whole with a specified number of layers
    • A63B37/0075—Three piece balls, i.e. cover, intermediate layer and core
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/36—Moulds for making articles of definite length, i.e. discrete articles
    • B29C43/3642—Bags, bleeder sheets or cauls for isostatic pressing
    • B29C2043/3644—Vacuum bags; Details thereof, e.g. fixing or clamping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B29C43/30—Making multilayered or multicoloured articles
    • B29C43/305—Making multilayered articles

Definitions

  • This invention relates generally to golf balls, and more specifically, to a multilayer golf ball.
  • this invention relates to a golf ball having a core, a cover and one or more mantle layers disposed between the core and cover.
  • This invention is also directed to a composition used for the manufacture of golf ball cores, mantle layers and covers for the multilayer golf ball.
  • the multilayer golf balls of the present invention have been found to provide the distance and durability characteristics approaching that of a conventional two piece ball while also providing good feel.
  • Conventional golf balls can be divided into two general types or groups: two piece balls or wound balls (also know as three piece balls) .
  • the difference in play characteristics resulting from these different types of constructions can be quite significant.
  • Balls having a two piece construction are generally most popular with the average recreational golfer because they provide a very durable ball while also providing maximum distance.
  • Two piece balls are made with a single solid core, usually made of a crosslinked rubber, which is encased by a cover material.
  • the solid core is made of polybutadiene which is chemically crosslinked with zinc diacrylate and/or similar crosslinking agents and is covered by a tough, cut-proof blended cover.
  • the cover is generally a material such as SURLYN ® , which is a trademark for an ionomer resin produced by DuPont.
  • SURLYN ® which is a trademark for an ionomer resin produced by DuPont.
  • such a combination imparts a high initial velocity to the ball which results in improved distance. Because these materials are very rigid, two piece balls have a hard "feel" when struck with a club. Likewise, due to their hardness, these balls have a relatively low spin rate which provides greater distance.
  • Wound balls typically have either a solid rubber or liquid center core around which many yards of a stretched elastic thread or yarn are wound.
  • the wound core is then covered with a durable cover material such as a SURLYN ® or similar material or a softer cover such as Balata or polyurethane.
  • Wound balls are generally softer and provide more spin, which enables a skilled golfer to have more control over the ball's flight and final position.
  • the high spin rate of soft, wound balls enables the golfer to stop the ball very near its landing position.
  • players generally seek a golf ball that delivers maximum distance, which requires a high initial velocity upon impact. Therefore, in an effort to meet the demands of the marketplace, manufacturers strive to produce golf balls with initial velocities in the USGA test that approximate the USGA maximum of 77.7 m/s or 255 ft/s as closely as possible. Therefore, golf ball manufacturers are continually searching for new ways in which to provide golf balls that deliver the maximum performance for golfers of all skill levels, and seek to discover compositions that provide the performance of a high compression ball with lower compression.
  • a number of polymers such as polybutadiene, natural rubber, styrene butadiene, and isoprene, are commonly used in fabricating golf ball cores.
  • manufacturers have added cross-linking agents, such as metallic salts of an unsaturated carboxylic acid.
  • the amount of cross-linking agent added is typically about 20 to 50 parts per hundred parts of polybutadiene.
  • zinc diacrylate or zinc dimethacrylate are used for this purpose. Of these two cross-linkers, zinc diacrylate has been found to produce golf balls with greater initial velocity than zinc dimethacrylate.
  • zinc oxide ZnO
  • This material serves as both a filler and an activation agent for the zinc diacrylate/peroxide cure system.
  • the zinc diacrylate/peroxide cure system which is well known to those of ordinary skill in this art, cross-links the polybutadiene during the core molding process.
  • the high specific gravity of zinc oxide (5.57) can serve the dual purposes of adjusting the weight of the golf ball, in addition to acting as an activation agent.
  • a golf ball core composition with an activation agent other than zinc oxide i.e., wherein all or at least some of the zinc oxide commonly present was eliminated, which would, as noted above, provide a ball with a lower compression, but would maintain the velocity and distance of a high compression ball.
  • the present invention provides such a golf ball core.
  • This golf ball has a center portion and the outer layer formed from a rubber composition, preferably having a base rubber of polybutadiene, wherein the outer layer further contains a gravity filler such as tungsten or tungsten carbide so as to impart a higher specific gravity to the outer layer than tha € of the inner layer.
  • the difference in specific gravity of the layers should be 0.15-0.8 for small balls and 0.15-0.45 for large balls.
  • the outer layer is harder than the center portion.
  • U.S. Patent No. 5,184,828 relates to a solid three- piece golf ball having improved rebound characteristics and carry distance while maintaining an adequate spin rate. These characteristics are obtained by controlling the size of the inner core and outer layer as well as the specific gravity and hardness.
  • the core and mantle layers are made from a rubber compound such as polybutadiene, and have a Shore D hardness of 30-62 and 30-56 respectively.
  • the key to obtaining the desired rebound characteristics is that the maximum hardness (42-62) must be located at the interface between the core and the mantle and the hardness must then decrease both inwardly and outwardly.
  • U.S. Patent No. 4,714,253 is also directed towards a three-piece golf ball having an excellent rebound coefficient.
  • This golf ball has a core with a Shore C hardness of 57-80 in its center, but not more than 83 at a distance between 5-10mm from its center and an outer layer with a Shore C hardness of 70-83.
  • U.S. Patent No. 5,072,944 discloses a three-piece solid golf ball having a center and outer layer which are prepared from a rubber composition, preferably having a base rubber of polybutadiene. It is desirable that the center core is softer than the outer layer, each having a hardness (Shore C) of 25-50 and 70-90 respectively.
  • U.S. Patent No. 4,625,964 relates to a solid golf ball having a polybutadiene rubber core of a diameter not more than 32mm, and a polybutadiene rubber intermediate layer having a specific gravity of lower than that of the core material, and a cover.
  • U.S. Patent No. 4,650,193 is directed towards a solid golf ball having a core comprising of a central portion and an integral outer layer.
  • the core is a curable elastomer such as polybutadiene which is treated with a cure altering agent to soften an outer layer of the core, thereby producing a central layer with a hardness (Shore C) of greater than 75 and an outer layer with a hardness (Shore A) of less than 80.
  • U.S. Patent No. 4,848,770 discloses a non-wound three-piece golf ball which includes a core of a highly filled synthetic rubber or polymeric material, an intermediate mantle of an unfilled synthetic rubber and a cover.
  • the core and intermediate mantle have a hardness of between 50-95.
  • U.S. Patent No. 5,002,281 is directed towards a three-piece solid golf ball which has an inner core having a hardness of 25-70 (Shore C) , an outer shell having a hardness of 80-95 (Shore C) and a cover. Further, the specific gravity of the inner core must be greater than 1.0, but less than or equal to that of the outer shell, which must be less than 1.3.
  • U.S. Patent No. 5,253,871 concerns a golf ball having a three piece structure comprising an elastomer core, an intermediate layer of a thermoplastic material containing at least 10% of ether block copolymer, preferably blended with an ionomer and a thermoplastic cover.
  • U.S. Patent No. 4,431,193 relates to a golf ball having a multilayer cover wherein the inner layer is a hard, high flexural modulus ionomer resin and the outer layer is a soft, low flexural modulus ionomer resin, and wherein either or both layers may comprise a foamed ionomer resin.
  • U.S. Patent No. 5,314,187 also relates to golf balls having a multiple layer cover, wherein the outer layer is molded over the inner layer and comprises a blend of balata and an elastomer and the inner layer is an ionomer resin.
  • U.S. Patent No. 4,919,434 is directed towards a golf ball having a cover which comprises an inner layer and an outer layer each of which comprise a thermoplastic resin, preferably the layers comprise of materials that are capable of fusion bonding with each other.
  • the present invention is directed towards a multilayer golf ball which provides a softer feel similar to a conventional wound ball, while also providing the distance, durability and relative ease of manufacturing of a conventional two piece ball.
  • the prior art has been directed at making golf balls perform like a three piece ball by providing a softer cover.
  • the present invention is directed to a golf ball that has durability, a low spin rate and substantial distance more like a conventional two piece ball, but has a soft feel by using a soft, high specific gravity mantle layer and a soft core.
  • the present invention is further directed towards a multi-layer golf ball which comprises a core with one or more layers; at least one cover layer; and one or more mantle layers disposed between the core and cover layer.
  • the core is preferably comprised of a polybutadiene rubber having an activation agent of calcium oxide.
  • the mantle layer preferably comprises thermoplastic copolyetherester block copolymer, thermoplastic copolyesterester block copolymer, thermoplastic polyurethane, thermoset polyurethane, dynamically vulcanized thermoplastic elastomer, styrene- butadiene, styrene-isoprene and styrene-ixoprene elastomers with a functional group such as maleic anhydride or sulfonic acid, polymer made using a metallocene catalyst, or blends thereof and/or thermoset-materials and includes a filler to increase the specific gravity.
  • the cover preferably comprises a thermoplastic or thermosetting material and, preferably, includes a filler to increase the specific gravity.
  • the present invention is still further directed to a multi-layer golf ball which comprises a core, at least one cover layer and at least one mantle layer disposed between the core and cover layer wherein properties such as the thickness, specific gravity, hardness, flexural modulus, tensile modulus, compression or Bashore resilience of the various layers is such as to provide a ball with distance performance characteristics and a soft feel.
  • the present invention is also directed to an improved multilayer golf ball having a softer golf ball core.
  • the composition of the golf ball core comprises a base mixture of polybutadiene, a metal salt diacrylate or dimethacrylate, preferably, zinc diacrylate in an amount of about 20 to 50 parts per hundred parts of polybutadiene, and a free radical initiator, to which calcium oxide (CaO) is added instead of zinc oxide as an activation agent in an amount sufficient to produce a golf ball core with the advantageous properties discussed below.
  • CaO calcium oxide
  • the calcium oxide can be added in an amount that reduces the compression of the golf ball, while maintaining the initial velocity of the ball in the USGA test.
  • calcium oxide can be used in conjunction with an increased amount of zinc diacrylate to maintain a consistent compression and increased initial velocity.
  • I ( incorporated into the core composition of the invention is between about 0.1 and 15 -parts per 100 parts of polybutadiene.
  • the amount of calcium oxide used is preferably less than about 15 pph because when more than 15 pph is used there appears to be a large decrease in the golf ball core compression that results in a significant reduction in the initial velocity of balls incorporating such cores.
  • fillers have been removed from the core and have been added to the mantle layer and/or the cover.
  • the spin rate of the ball is decreased.
  • the compression of the ball is decreased by removing the fillers from the core and adding them to the mantle layer and cover. This improves the feel of the golf ball.
  • the invention thus provides a novel golf ball composition that offers the environmental benefit of eliminating or at least reducing the use of zinc oxide, while providing a golf ball with enhanced performance properties.
  • FIG. 1 is a cross-sectional view of a golf ball according to the present invention.
  • Fig. 2 is a perspective view of a golf ball according to the present invention.
  • reaction conditions can refer to any reaction condition that can affect the ability of the inventive core compositions to form free radicals.
  • Reaction conditions 0 include, for example, temperature, time and pressure.
  • points or “compression points” refer to the compression scale or the compression scale based on the ATTI Engineering Compression Tester. This scale, which is well known to those working in this field, is 5 used in determining the relative compression of a core or ball. Some artisans use the Reihle compression scale instead of the standard compression scale. Based on disclosure in U.S. Patent No. 5,368,304, column 20, lines 55-53 it appears that Reihle compression values can be converted to 0 compression values through the use of the following equation:
  • this invention is 5 particularly directed towards a multi-layer golf ball 1 which comprises a core 2 , at least one cover layer 3 and at least one mantle layer 4 disposed therebetween.
  • Tests were carried out using a 0.2 in/min cross-head speed Q and a 2 inch span length in the three point bending mode. Test samples were annealed at 140°F for 24 hours and the tests were performed no earlier than 24 hours after annealing.
  • Tests were carried out on type IV specimens using a 2 in/min cross-head speed without an extensiometer. Test samples were annealed at 140°F for 24 hours and the tests were performed 5 no earlier than 24 hours after annealing.
  • a representative base composition for forming the golf ball core 2, prepared in accordance with the present invention comprises polybutadiene and, in parts by weight based on 100 parts polybutadiene, 20-50 parts of a metal salt diacrylate, dimethacrylate, or mono ethacrylate, preferably zinc diacrylate.
  • the polybutadiene preferably has a cis 1,4 content of above about 90% and more preferably above about 96%.
  • Commercial sources of polybutadiene include Shell 1220 manufactured by Shell Chemical, Neocis BR40 manufactured by Enichem Elastomers, and Ubepol BR150 manufactured by Ube Industries, Ltd.
  • the polybutadiene can also be mixed with other elastomers known in the art, such as natural rubber, styrene butadiene, and/or isoprene in order to further modify the properties of the core.
  • elastomers known in the art, such as natural rubber, styrene butadiene, and/or isoprene.
  • the amounts of other constituents in the core composition are usually based on 100 parts by weight of the total elastomer mixture.
  • Metal salt diacrylates, dimethacrylates, and monomethacrylates suitable for use in this invention include those wherein the metal is magnesium, calcium, zinc, aluminum, sodium, lithium or nickel.
  • Zinc diacrylate is preferred, because it provides golf balls with a high initial velocity in the USGA test.
  • the zinc diacrylate can be of various grades of purity. For the purposes of this invention, the lower the quantity of zinc stearate present in the zinc diacrylate the higher the zinc diacrylate purity. Zinc diacrylate containing less than about 10% zinc stearate is preferable. More preferable is zinc diacrylate containing about 4-8% zinc stearate.
  • Suitable, commercially available zinc diacrylates include those from Rockland React-Rite and Sarto er.
  • the preferred concentrations of zinc diacrylate that can be used are 20-50 pph based upon 100 pph of polybutadiene or alternately, polybutadiene with a mixture of other elastomers that equal 100 pph.
  • Free radical initiators are used to promote cross-linking of the metal salt diacrylate, dimethacrylate, or monomethacrylate and the polybutadiene.
  • Suitable free radical initiators for use in the invention include, but are not limited to peroxide compounds, such as dicumyl peroxide, 1,1-di (t-butylperoxy) 3 , 3 , 5-trimethyl cyclohexane, a-a bis (t-butylperoxy) diisopropylbenzene, 2 , 5-dimethyl-2 , 5 di (t-butylperoxy) hexane, or di-t-butyl peroxide, and mixtures thereof.
  • peroxide compounds such as dicumyl peroxide, 1,1-di (t-butylperoxy) 3 , 3 , 5-trimethyl cyclohexane, a-a bis (t-butylperoxy) diisopropylbenzene, 2 , 5-dimethyl-2 , 5 di (t-butylperoxy) hexane, or di-t-butyl peroxide, and mixtures thereof.
  • Other useful initiators would
  • the initiator (s) at 100% activity are preferably added in an amount ranging between about 0.05 and 2.5 pph based upon 100 parts of butadiene, or butadiene mixed with one or more other elastomers. More preferably, the amount of initiator added ranges between about 0.15 and 2 pph and most preferably between about 0.25 and 1.5 pph.
  • a typical prior art golf ball core incorporates 5 to 50 pph of zinc oxide in a zinc diacrylate-peroxide cure system that cross-links polybutadiene during the core molding process.
  • the zinc oxide (ZnO) is eliminated in favor of calcium oxide (CaO) in the golf ball core composition.
  • the cores and balls produced from such an admixture typically exhibit enhanced performance properties.
  • the initial velocity of the standard ball is maintained at or near the maximum allowed by the USGA, but the compression of the ball is reduced by at least about 2 compression points on the standard compression scale, and may be reduced as much as 14 points.
  • the combination of the use of calcium oxide and a higher percentage of zinc diacrylate can be used to maintain the same compression as with the zinc oxide, but the initial velocity is significantly increased.
  • the amount of zinc oxide incorporated in prior art cores is, as noted above, typically about 5 to 50 pph
  • the amount of calcium oxide added to the core-forming composition of the invention as an activator is typically in the range of about 0.1 to 15, preferably 1 to 10, most preferably 1.25 to 5, parts calcium oxide per hundred parts (pph) of polybutadiene.
  • the compositions of the present invention may also include fillers, added to the elastomeric composition to adjust the density and/or specific gravity of the core.
  • fillers includes any compound or composition that can be used to vary the density and other properties of the subject golf ball core.
  • Fillers useful in the golf ball core according to the present invention include, for example, zinc oxide (in an amount significantly less than that which would be necessary without the addition of the calcium oxide) , barium sulfate, and regrind (which is recycled core molding matrix ground to 30 mesh particle size) .
  • the amount and type of filler utilized is governed by the amount and weight of other ingredients in the composition, since a maximum golf ball weight of 1.620 ounces (45.92 gm) has been established by the USGA.
  • Appropriate fillers generally used range in specific gravity from about 2.0 to 5.6. In the preferred golf ball, the amount of filler is lower than that of a typical golf ball such that the specific gravity of the core is decreased.
  • the filler removed from the core is added to the mantle layer and/or the cover of the preferred golf ball.
  • the golf ball core 2 as shown in Fig. 1, in typical prior art golf balls has a specific gravity of about 1.2 to 1.5.
  • the preferred range of specific gravities of the present invention is from about 1.0 to about 1.2, more preferably in the range of about 1.1 to about 1.18, depending upon the size of the core, cover, mantle layer and finished ball, as well as the specific gravity of the cover and mantle layer.
  • Antioxidants may also be included in the elastomer cores produced according to the present invention.
  • Antioxidants are compounds which prevent the breakdown of the elastomer.
  • Antioxidants useful in the present invention include, but are not limited to, quinoline type antioxidants, amine type antioxidants, and phenolic type antioxidants.
  • Other ingredients such as accelerators, e.g. tetra methylthiuram, processing " aids, processing oils, plasticizers, dyes and pigments, as well as other additives well known to the skilled artisan may also be used in the present invention in amounts sufficient to achieve the purpose for which they are typically used.
  • the core compositions of the invention are produced by forming a mixture comprising at least polybutadiene, zinc diacrylate, and calcium oxide.
  • Either the calcium oxide is used to reduce the compression by at least about 2 points on the compression scale, compared to a core composition having zinc oxide or the amount of zinc diacrylate is increased such that the compression is the same, but the initial velocity is increased.
  • calcium oxide either the ball compression can be lowered and the initial velocity maintained or the amount of zinc diacrylate can be increased so that the ball compression is the same and the initial velocity is increased.
  • the free radical initiator is added in an amount dependent upon the amounts and relative ratios of the starting components, as would be well understood by one of ordinary skill in the art.
  • the resultant shear causes the temperature of the mixture to rise.
  • Peroxide (s) free radical initiator (s) are blended into the mixture for crosslinking purposes in the molding process.
  • the golf ball core composition is milled and hand prepped or extruded into pieces ("preps") suitable for molding.
  • the milled preps are then compression molded into cores at an elevated temperature. Typically, 160°C (320°F) for 15 minutes is suitable for this purpose.
  • These cores can then be used to make finished golf balls by surrounding the cores with mantle and cover materials.
  • Table I sets forth the contents of the golf ball cores that were made to illustrate the effect of using calcium oxide instead of zinc oxide.
  • the control core and Examples 1-3 all contain zinc oxide.
  • Example 4 was made without zinc oxide or calcium oxide and Examples 5-9 were made with different amounts of calcium oxide.
  • the compositions used to prepare the golf ball cores of these examples are all in parts per hundred (pph) , based on 100 parts of polybutadiene.
  • the fillers used in the compositions of these examples are regrind and barium sulfate (BaS0 4 ) .
  • Vulcup 40KE ® and Varox 231XL ® are free radical initiators, and are a-a bis (t-butylperoxy) diisopropylbenzene and 1,1-di (t-butylperoxy) 3 , 3 , 5-trimethyl cyclohexane, respectively.
  • Yel MB is a yellow pigment in a styrene butadiene binder, which is used to color the composition for identification purposes.
  • the zinc diacrylate contained no more than about 4-8% zinc stearate.
  • the cores and balls prepared according to the above-described method were tested for their compression and initial velocity.
  • the compression ratings were obtained using a commercial compression tester.
  • the initial velocity results were obtained from a standard technique, whereby the cores or balls are struck at 39.6 m/s (130 ft/s), and pass through light gates, which measure their speed. Both of these standard measurement techniques are well-known to those of ordinary skill in the art of making golf ball cores and balls.
  • Example 4 reduces the compression of both the core and the ball by a significant amount, greater than 10 points, but also reduces the initial velocity of the core and ball significantly, approximately one mile per hour.
  • the zinc oxide is eliminated from the core composition, and calcium oxide is added in Examples 5-8, both the cores and finished balls containing calcium oxide have a lower compression, but the initial velocity of the low compression balls and cores is comparable to that of the high compression control ball.
  • Table III illustrates the effect of varying amounts of calcium oxide, zinc oxide and zinc diacrylate in golf ball cores on compression ratings and initial velocity.
  • Examples A-D below are multilayer balls having a Hytrel ® 3078 mantle layer and SURLYN ® covers made of 50% high acid SURLYN ® and 50% standard SURLYN ® .
  • Each of the balls has a 1.39 inch diameter polybutadiene core made with the compositions listed.
  • the results show that the compression can be decreased for a ball made with zinc oxide by decreasing the percentage of zinc diacrylate as shown by the comparison of Examples A and B. However, by decreasing the zinc diacrylate, the ball initial velocity was decreased.
  • Examples B and C the effect of substituting calcium oxide for zinc oxide is shown.
  • Example C has a lower compression and higher initial velocity than the ball with zinc oxide, Example B.
  • Examples D and B show that by using calcium oxide with an increased amount of zinc diacrylate the compression can be decreased and the initial velocity substantially increased.
  • Table III both balls having calcium oxide, Examples C and D, exhibit a very low compression, below 80, and high initial velocity.
  • mantle layer 4 preferably comprises thermoplastic copolyesterester block copolymer
  • thermoplastic elastomer styrene- butadiene elastomer with functional groups such as maleic anhydride or sulfonic acid attached, thermoplastic polyurethane or polymers made using a metallocene catalyst or blends thereof.
  • the mantle layer 4 is a thermoplastic copolyetherester block copolymer.
  • Suitable thermoplastic copolyetheresters include Hytrel ® 3078, Hytrel ® G3548W and Hytrel ® G4078W which are commercially available from DuPont.
  • Hytrel ® 3078 being the
  • Prior art mantle layers generally have a specific gravity of about 1 or less. As stated above, the objective of most prior art multi-layer balls is to increase spin.
  • the mantle layer according to the present invention preferably
  • the specific gravity of the mantle layer is increased to about 1.25 by adding about 20% of a filler such as barium sulfate, zinc oxide, titanium dioxide and combinations thereof.
  • the most preferred golf ball is comprised of a mantle layer made of Hytrel ® 3078 and 20% zinc oxide.
  • Suitable dynamically vulcanized thermoplastic elastomers include Santoprene ® , Sarlink ® , Vyram ® , Dytron ® and Vistaflex ® .
  • Santoprene ® is the trademark for a dynamically vulcanized PP/EPDM.
  • Santoprene ® 203-40 is an example of a preferred Santoprene ® and is commercially available from Advanced Elastomer Systems.
  • Suitable functionalized styrene-butadiene elastomers i.e., styrene- butadiene elastomers with functional groups such as maleic anhydride or sulfonic acid
  • suitable thermoplastic polyurethanes include Estane ® 58133, Estane ® 58134 and Estane ® 58144, which are commercially available from the B.F. Goodrich Company.
  • Suitable metallocene polymers i.e., polymers made with a metallocene catalyst, whose melting points are higher than the cover materials can also be employed in the mantle layer of the present invention.
  • the materials for the mantle layer described above may be in the form of a foamed polymeric material.
  • suitable metallocene polymers include foams of thermoplastic elastomers based on metallocene single-site catalyst-based foams. Such metallocene-based foam resins are commercially available from Sentinel Products of Hyannis, Massachusetts.
  • the mantle layer is a blend of a first and a second thermoplastic, wherein the first thermoplastic is a thermoplastic copolyetherester or copolyesterester block copolymer, a dynamically vulcanized thermoplastic elastomer, a functionalized styrene-butadiene elastomer, a thermoplastic polyurethane or a metallocene polymer and the second thermoplastic is a material such as a thermoplastic polyurethane, a thermoplastic polyetherester or polyetheramide, a thermoplastic ionomer resin, a thermoplastic polyester, another dynamically vulcanized elastomer, another functionalized styrene-butadiene elastomer, another metallocene polymer or blends thereof.
  • the first thermoplastic is a thermoplastic copolyetherester or copolyesterester block copolymer
  • a dynamically vulcanized thermoplastic elastomer a functionalized styren
  • Suitable thermoplastic polyetheresters include Hytrel ® 3078, Hytrel ® G3548W and Hytrel ® G4078W which are commercially available from DuPont.
  • Suitable thermoplastic polyetheramides include Pebax ® 2533, Pebax ® 1205 and
  • thermoplastic ionomer resins include any number of olefinic based ionomers including SURLYN ® 8320, 8269 and 8265, which are commercially available from DuPont. The flexural moduli for these ionomers is less than about 10 kpsi.
  • Suitable thermoplastic polyesters include polybutylene terephthalate.
  • the dynamically vulcanized thermoplastic elastomers, functionalized styrene-butadiene elastomers, thermoplastic polyurethane or metallocene polymers identified above are also useful as the second thermoplastic in such blends. Further, the materials of the second thermoplastic described above may be in the form of a foamed polymeric material.
  • the cover layers of the present invention comprises at least one layer of a thermoplastic or ther osetting material.
  • cover materials may be used in the present invention.
  • ionomer resins include E/X/Y copolymers where E is ethylene, X is a softening comonomer such as acrylate or methacrylate present in 0-50 (preferably 0-25, most preferably 0-2) , weight percent of the polymer, and Y is acrylic or methacrylic acid present in 5-35 (preferably 10- 35, most preferably 15-20) weight percent of the polymer, wherein the acid moiety is neutralized 1-90% (preferably at least 40%, most preferably at least about 60%) to form an ionomer by a cation such as lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc or aluminum, or a combination of such cation, lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc or aluminum, or a combination of such cation, lithium, sodium
  • Specific acid-containing ethylene copolymers include ethylene/acrylic acid, ethylene/methacrylic acid, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/n-butyl acrylate, ethylene/methacrylic acid/iso-butyl acrylate, ethylene/acrylic acid/iso-butyl acrylate, ethylene/methacrylic acid/n-butyl methacrylate, ethylene/acrylic acid/methyl methacrylate, ethylene/acrylic acid/methyl acrylate, ethylene/methacrylic acid/methyl acrylate, ethylene/methacrylic acid/methyl methacrylate, and ethylene/acrylic acid/n-butyl methacrylate.
  • Preferred acid- containing ethylene copolymers include ethylene/methacrylic acid, ethylene/acrylic acid, ethylene/methacrylic acid/n- butyl acrylate, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/methyl acrylate and ethylene/acrylic acid/methyl acrylate copolymers.
  • the most preferred acid-containing ethylene copolymers are ethylene/methacrylic acid, ethylene/acrylic acid, ethylene/ (meth) acrylic acid/n-butyl acrylate, ethylene/ (meth) acrylic acid/ethyl acrylate, and ethylene/ (meth) acrylic acid/methyl acrylate copolymers.
  • SURLYN ® a presently preferred cover material
  • SURLYN ® 8140 and SURLYN ® 7940 which are a sodium ionomer made with 19% methacrylic acid and a lithium ionomer made with 15% methacrylic acid, respectively.
  • This cover material has a flexural modulus of about 85 ksi.
  • Another preferred cover is comprised of a 50/50 blend of SURLYN ® 8140 and SURLYN ® AD 8546 (SEP671) , which is a lithium SURLYN ® having about 19% methacrylic acid.
  • This material has a flexural modulus of about 105 ksi.
  • the flexural modulus of the cover is greater than 75 ksi.
  • the most preferred cover is comprised of a 50/50 blend of SURLYN ® AD 8546, which has about 19% methacrylic acid, and SURLYN ® 9910 which is a standard zinc SURLYN ® .
  • the preferred cover has a hardness of about 70 Shore D.
  • the high flexural modulus of the cover provides increased initial velocity for extra distance.
  • SURLYN ® covers have a specific gravity of about .96.
  • the cover according to the present invention is further comprised of a filler such as barium sulfate, zinc oxide, titanium oxide, or combinations thereof mixed into the thermoplastic or thermosetting material.
  • the specific gravity is preferably increased from about .96 to about 1.25 to increase the balls moment of inertia and reduce the golf ball's initial spin rate.
  • the cover layer comprises an inner layer and an outer layer.
  • the inner layer of the cover is either a thermoplastic material such as a thermoplastic elastomer or a thermoplastic rubber, or a thermoset rubber or thermoset elastomer material.
  • materials suitable for use as the inner cover layer include polyether or polyester thermoplastic urethanes as well as thermoset polyurethanes.
  • a preferable thermoplastic material is a thermoplastic urethane with a melting point of about 178° to about 205°F.
  • a preferable thermoset material is a rubber based, castable urethane.
  • the outer layer of the cover is either a thermoplastic plastic material such as an elastomer or a thermoplastic rubber, or a thermosetting material.
  • Suitable materials for the outer layer include Urethanes, ionomers with a low modulus and other "dead” but durable materials such as EPDM and butyl rubber. Additionally, the present invention also contemplates the use of a polymeric foam material, such as the metallocene-based foamed resin described above, as the material for either the outer cover layer or the inner cover layer, but preferably not both layers.
  • thermoplastic or thermosetting materials of the outer layer have a melting point or reaction (cure) temperature less than the melting point or reaction (cure) temperature of the materials of the inner layer.
  • the present invention also contemplates the use of a variety of non-conventional cover materials.
  • the covers of the present invention may comprise thermoplastic or engineering plastics such as ethylene or propylene based homopolymers and copolymers including functional monomers such as acrylic and methacrylic acid and fully or partially neutralized ionomers and their blends, methyl acrylate, methyl methacrylate homopolymers and copolymers, imidized, amino group containing polymers, polycarbonate, reinforced polya ides, polyphenylene oxide, high impact polystyrene, polyether ketone, polysulfone, poly (phenylene sulfide) , reinforced engineering plastics, acrylonitrile-butadiene, acrylic-styrene-acrylonitrile, poly (ethylene terephthalate) , poly (butylene terephthalate) , poly (ethylene-vinyl alcohol), poly (tetrafluoroethylene) and their copolymers including functional comonomers
  • the thickness of the mantle layer of the present invention is about 0.025 inches to about 0.125 inches.
  • the thickness of the mantle layer is about 0.04 inches to about 0.10 inches.
  • the thickness of the mantle layer is about 0.06 inches.
  • the diameter of the core of the present invention is about 1.25 inches to about 1.51 inches.
  • the diameter of the core is"about 1.30 inches to about 1.48 inches.
  • the diameter of the core is about 1.39 inches.
  • the overall diameter of the core and mantle layer is about 84% to about 97% of the overall diameter of the finished ball, and is preferably about 1.51 inches.
  • the specific gravity of the core is less than about 1.2 and, more preferably, less than about 1.16.
  • the mantle layer and/or the cover preferably have specific gravities greater than about 1.2 and, most preferably, about 1.25.
  • Table IV provides test data to show the decrease in spin rate for golf balls according to the present invention.
  • the golf balls in Examples 1 and 2 are comprised of cores made of polybutadiene with zinc oxide, mantle layers made of Hytrel ® 3078 and covers made of a blend of SURLYN ® 7930 and 8920.
  • the ball in Example 2 has a low weight core and heavy mantle and cover layers according to the present invention.
  • 20% and 30% of barium sulfate was added to the mantle layer and cover, respectively.
  • the compression of the core is decreased from the removal of the fillers, which contributes to the decreased initial spin rate.
  • the driver spin rate of the Example 2 ball is almost 200 rpm less than the Example 1 ball and the 8 iron spin rate is almost 500 rpm less.
  • the ball in Example 2 is much softer and has a better feel than the ball in Example 1.
  • the removal of the fillers from the core decreases the ball compression by at least 5 compression points and, most preferably, decreases the compression of the core so that the compression of the ball is about 80 or less.
  • the initial velocity is increased by- removing the filler from the core and adding it to the mantle and/or the cover.
  • filler was removed from the core in Example 3 and added to the mantle layer in Example 4.
  • the mantle layer of Example 4 was comprised of Hytrel ® 3078 and 20% zinc oxide.
  • the initial velocity of the ball in Example 4 is higher than the ball in Example 3, and the spin rates are less.
  • the present multi-layer golf ball can have an overall diameter of any size. Although the United States Golf Association (USGA) specifications limit the minimum size of a competition golf ball to 1.680 inches in diameter or more, there is no specification as to the maximum diameter. Moreover, golf balls of any size can be used for recreational play.
  • the preferred diameter of the present golf balls is from about 1.680 inches to about 1.800 inches. The more preferred diameter is from about 1.680 inches to about 1.760 inches. The most preferred diameter is about 1.680 inches to about 1.740 inches.
  • the flexural and/or tensile moduli of the mantle layer are believed to have an effect on the "feel" of the golf balls of the present invention. Accordingly, it is preferable that the golf balls of the present invention have a mantle layer with a flexural modulus of about 500 psi to about 50,000 psi in order to impart a softer "feel" to the golf balls of the present invention. Likewise, it is preferred that the mantle layer have a tensile modulus of about 500 psi to about 50,000 psi in order to impart a softer "feel" to the golf balls of the present invention.
  • the flexural modulus and tensile modulus of the mantle layer are both less than about 10,000 psi. Most preferably, the flexural modulus of the mantle layer is less than 5000 psi. Further, the core of the present invention has a
  • the core has a Bashore resilience of about 40 to about 70.
  • the mantle layer of the present invention has a Bashore resilience of about 35 to about 75.
  • the mantle layer has a Bashore resilience of about 60-70.
  • the golf balls of the present invention have a mantle layer with a Shore D hardness of less than about 60.
  • the Shore D hardness of the mantle layer is about 20 to about 60.
  • the mantle layer has a Shore D hardness of about 30 to provide the soft "feel" desired.
  • the core has a Shore D hardness of about 30 to about 65.
  • the core has a Shore D hardness of about 35 to about 60 and a compression less than 60 such that the ball compression is less than about 90.
  • the core compression is low enough to make the ball compression less than or equal to about 80.
  • the golf balls of the present invention can be made by any conventional process employed in the golf ball art.
  • the solid cores can be either injection or compression molded.
  • the undersized wound cores of the present invention are produced through conventional means.
  • the mantle layer is subsequently injection or compression molded about the core. It is important that the mantle material be able to sustain the temperatures applied during the application of the cover layer.
  • the cover layer or layers are then injection or compression molded or cast about the mantle layer.
  • the core is preferably compression molded as stated above.
  • the mantle layer is molded over the core using a retractable-pin mold or a fixed-pin mold.
  • a plurality of apertures are formed in the mantle layer to form a mechanical interlock with the cover.
  • the cover is molded over the mantle layer.
  • Table VI Illustrated in Table VI are a number of batch formulations for several mantle layer compositions of the present invention, as well as properties such a hardness (Shore D) , Bashore resilience, flexural modulus, % strain at break and tensile modulus for each composition.
  • properties such as a hardness (Shore D) , Bashore resilience, flexural modulus, % strain at break and tensile modulus for each composition.
  • Tables VII and VIII provide test data obtained from balls having soft mantle- layers.
  • the spin rate and velocity were measured for golf balls formed according to the present invention.
  • the mantle layer was Hytrel 3078
  • the cover was a conventional lithium/high acid sodium SURLYN ® 50/50 blend (SURLYN 7940/SURLYN 8140) and the core was a conventional crosslinked polybutadiene core.
  • the mantle layer was Hytrel 3078
  • the cover was high acid lithium/standard zinc 50/50 blend (SURLYN ® SEP 671/SURLYN ® 9910) and the core was a polybutadiene core with 2.13 pph calcium oxide.
  • Both cores had a diameter of 1.39 inches and a specific gravity of about 1.25.
  • the mantle layers were 0.06 inches thick and the covers were 0.085 inches thick.
  • Convention two piece golf balls (Titleist HVC 90 and Pinnacle Gold) for comparison. Each ball was tested in a True Temper Test Machine. The test machine was configured to strike the balls with a Driver and an Eight Iron.
  • golf balls having a low modulus mantle layer- like Hytrel 3078, have a high initial velocity and low spin rate for good distance.
  • the ball having calcium oxide in the core composition has a very soft "feel", more like a wound ball.
  • these balls are easy to manufacture compared to the conventional wound ball.
  • these balls provide the advantages of two piece balls with low spin rates, high velocity and soft "feel”.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

Cette invention a trait à une balle de golf multicouche (1) constituée d'un noyau (2), d'au moins une couche de couverture (3) et d'une ou de plusieurs couches d'enveloppe (4) situées entre le noyau (2) et la couche de couverture (3). La couche d'enveloppe (4) est constituée de copolymère séquencé de co-polyéther-ester thermoplastique, de copolymère séquencé de co-polyester-ester thermoplastique, d'élastomère thermoplastique vulcanisé de façon dynamique, d'élastomère butadiène-styrène fonctionnalisé, de polyuréthanne thermoplastique et de polymère métallocène ou de leurs mélanges ainsi que de matériaux et de matières de charge thermodurcissables, notamment du sulfate de baryum, de l'oxyde de zinc, du dioxyde de titane ou leurs mélanges. Cette invention concerne, de surcroît, une balle (1) dont le noyau (2) a une compression inférieure à 70, la couche d'enveloppe (4), un module d'élasticité en flexion inférieur à 10 000 psi et une densité supérieure à 1,2 environ, et la couche de couverture (3), un module d'élasticité en flexion supérieur à 75 000 psi.
PCT/US1997/020123 1996-11-08 1997-11-06 Balle de golf multicouche et composition WO1998019747A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP52173298A JP3607301B2 (ja) 1996-11-08 1997-11-06 多層ゴルフボール及び組成物
GB9910473A GB2333715B (en) 1996-11-08 1997-11-06 Multilayer golf ball
AU52460/98A AU5246098A (en) 1996-11-08 1997-11-06 Multilayer golf ball and composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/746,362 US5810678A (en) 1995-06-07 1996-11-08 Multilayer golf ball
US08/746,362 1996-11-08

Publications (1)

Publication Number Publication Date
WO1998019747A1 true WO1998019747A1 (fr) 1998-05-14

Family

ID=25000521

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/020123 WO1998019747A1 (fr) 1996-11-08 1997-11-06 Balle de golf multicouche et composition

Country Status (5)

Country Link
US (1) US5810678A (fr)
JP (1) JP3607301B2 (fr)
AU (1) AU5246098A (fr)
GB (1) GB2333715B (fr)
WO (1) WO1998019747A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1096977A1 (fr) * 1998-07-10 2001-05-09 Dunlop Sports Group Americas Inc. Balle de golf longue distance de type deux pieces
JP2003502123A (ja) * 1999-06-17 2003-01-21 スポルディング、スポーツ、ワールドワイド、インク 多層カバーを伴うゴルフボール
GB2362580B (en) * 1999-02-11 2003-12-10 Spalding Sports Worldwide Inc Low spin golf ball utilizing perimeter weighting
WO2014193777A1 (fr) * 2013-05-31 2014-12-04 Nike Innovate C.V. Balle de golf multicouche thermoplastique

Families Citing this family (118)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6315684B1 (en) 1992-04-24 2001-11-13 Spalding Sports Worldwide, Inc. Golf ball with soft core
US6325730B1 (en) 1992-04-24 2001-12-04 Spalding Sports Worldwide, Inc. Golf ball with soft core
US6413172B1 (en) 1992-04-24 2002-07-02 Spalding Sports Worldwide, Inc. Golf ball with soft core
US6422953B1 (en) 1992-04-24 2002-07-23 Spalding Sports Worldwide, Inc. Golf ball
US6193618B1 (en) * 1993-04-28 2001-02-27 Spalding Sports Worldwide, Inc. Low spin golf ball comprising a mantle with a cellular or liquid core
US6287217B1 (en) 1993-06-01 2001-09-11 Spalding Sports Worldwide, Inc. Multi-layer golf ball
US6663508B1 (en) 1993-06-01 2003-12-16 Callaway Golf Company Multi-layer golf ball with reaction injection molded polyurethane component
US6290614B1 (en) 1998-03-18 2001-09-18 Spalding Sports Worldwide, Inc. Golf ball which includes fast-chemical-reaction-produced component and method of making same
US6695718B2 (en) 1993-06-01 2004-02-24 The Top-Flite Golf Company Golf ball with sulfur cured inner core component
US6824476B2 (en) 1993-06-01 2004-11-30 Callaway Golf Company Multi-layer golf ball
US6210293B1 (en) 1993-06-01 2001-04-03 Spalding Sports Worldwide, Inc. Multi-layer golf ball
US6648777B2 (en) 1993-06-01 2003-11-18 Callaway Golf Company Multi-layer golf ball
US6638185B2 (en) 1993-06-01 2003-10-28 The Top-Flite Golf Company Multi-layer golf ball
US6432000B1 (en) 1993-06-01 2002-08-13 Spalding Sports Worldwide, Inc. Multilayer golf ball with filled inner layer having dual core, liquid core, or wound core
US6506130B2 (en) 1993-06-01 2003-01-14 Spalding Sports Worldwide, Inc. Multi layer golf ball
US5885172A (en) 1997-05-27 1999-03-23 Acushnet Company Multilayer golf ball with a thin thermoset outer layer
US7090798B2 (en) * 1997-05-27 2006-08-15 Acushnet Company Multilayer golf ball with a thin thermoset outer layer
US6677401B2 (en) 1995-01-24 2004-01-13 Acushnet Company Multi-layer golf ball with a thin, castable outer layer
US6124389A (en) * 1996-02-16 2000-09-26 Acushnet Company Multilayer golf ball and composition
US7131914B2 (en) * 1995-06-07 2006-11-07 Acushnet Company Method of making a golf ball with a multi-layer core
US7153467B2 (en) * 1995-06-07 2006-12-26 Acushnet Company Method of making a golf ball with a multi-layer core
US6355715B1 (en) 1995-06-07 2002-03-12 Acushnet Company Multi-layered golf ball and composition
US7014573B2 (en) 1995-06-07 2006-03-21 Acushnet Company Method of making a golf ball with a multi-layer core
US6494795B2 (en) * 2001-03-23 2002-12-17 Acushnet Company Golf ball and a method for controlling the spin rate of same
US5947842A (en) * 1995-06-07 1999-09-07 Acushnet Company Multi-layer low-spin golf ball
US6458892B1 (en) * 1995-06-07 2002-10-01 Acushnet Company Multilayer golf ball and composition
US7358305B2 (en) * 1995-06-07 2008-04-15 Acushnet Company Golf balls containing impact modified non-ionic thermoplastic polycarbonate/polyester copolymers or blends
US6786838B2 (en) 1995-06-07 2004-09-07 Acushnet Company Golf ball with multi-layered core
US7015300B2 (en) * 1995-06-07 2006-03-21 Acushnet Company Multilayered golf ball and composition
US6547677B2 (en) * 1995-06-07 2003-04-15 Acushnet Company Multi-layered core golf ball
US7594866B2 (en) * 1996-02-16 2009-09-29 Acushnet Company Method of making a golf ball with a multi-layer core
US6270429B1 (en) 1996-09-16 2001-08-07 Spalding Sports Worldwide, Inc. Crosslinked foam as filler in an inner layer or core of a multi-component golf ball
US20010019969A1 (en) * 1997-03-28 2001-09-06 Spalding Sports Worldwide, Inc. Perimeter weighted multi-layer golf ball
WO2000047670A1 (fr) * 1999-02-11 2000-08-17 Spalding Sports Worldwide, Inc. Balle de golf a faible effet rotatif comprenant un manteau ou une couche interieure metallique, ceramique ou composite
US6648776B1 (en) 1997-05-27 2003-11-18 Acushnet Company Multilayer golf ball with a thin thermoset outer layer
US7173088B2 (en) * 1997-05-27 2007-02-06 Acushnet Company Multi-layer golf ball with a thin, castable outer layer
US6486261B1 (en) * 1998-12-24 2002-11-26 Acushnet Company Thin-layer-covered golf ball with improved velocity
US6991563B2 (en) * 2001-03-23 2006-01-31 Acushnet Company Perimeter weighted golf ball
US6849006B2 (en) 1997-05-27 2005-02-01 Acushnet Company Thin, thermoset, polyurethane-covered golf ball with a dual core
US6812317B2 (en) * 1997-05-27 2004-11-02 Acushnet Company Wound golf ball having cast polyurethane cover
US20050070377A1 (en) * 1997-05-27 2005-03-31 Christopher Cavallaro Thin-layer-covered multilayer golf ball
US6634964B2 (en) 1997-05-27 2003-10-21 Acushnet Company Initial velocity dual core golf ball
US6913547B2 (en) 1997-05-27 2005-07-05 Acushnet Company Thin-layer-covered multilayer golf ball
US6716954B2 (en) 1998-03-18 2004-04-06 Callaway Golf Company Golf ball formed from a polyisocyanate copolymer and method of making same
US7067081B2 (en) * 1998-10-21 2006-06-27 Wilson Sporting Goods Co Method of making a golf ball product from fast-curling reaction injection molded polyurethane
US6293877B1 (en) * 1998-12-29 2001-09-25 Acushnet Company Golf ball
US6485378B1 (en) 1999-11-23 2002-11-26 Acushnet Company Golf ball
US7148266B2 (en) * 1999-12-23 2006-12-12 Callaway Golf Company Game balls with cover containing post crosslinkable thermoplastic polyurethane and method of making same
US6369125B1 (en) 1999-12-23 2002-04-09 Spalding Sports Worldwide, Inc. Game balls with cover containing post crosslinkable thermoplastic polyurethane and method of making same
US6398667B1 (en) 2000-06-08 2002-06-04 Wilson Sporting Goods Co. Golf ball with lattice structure
US6794447B1 (en) * 2000-07-28 2004-09-21 Taylor Made Golf Co., Inc. Golf balls incorporating nanocomposite materials
US8193283B2 (en) 2000-08-11 2012-06-05 E. I. Du Pont De Nemours And Company Golf balls with soft, resilient bimodal ionomeric covers
US6562906B2 (en) 2000-08-11 2003-05-13 E. I. Du Pont De Nemours And Company Bi-modal ionomers
US6458046B1 (en) 2000-08-21 2002-10-01 Acushnet Company Multi-layer, wound golf ball
US20020147057A1 (en) * 2001-02-06 2002-10-10 Spalding Sports Worldwide, Inc. Golf ball having very thin outermost cover layer for improved scuff resistance
US7022034B2 (en) * 2001-03-23 2006-04-04 Acushnet Company Golf ball having a non-uniform thickness layer
US6685580B2 (en) 2001-03-23 2004-02-03 Acushnet Company Three-layer cover for a golf ball including a thin dense layer
US6685579B2 (en) 2001-04-10 2004-02-03 Acushnet Company Multi-layer cover polyurethane golf ball
US6852042B2 (en) * 2001-03-23 2005-02-08 Acushnet Company Golf ball
US7357735B2 (en) * 2001-03-23 2008-04-15 Acushnet Company Fully-neutralized ionomers for use in golf ball having a large core and a thin, dense layer
US6743123B2 (en) * 2001-03-23 2004-06-01 Acushnet Company Golf ball having a high moment of inertia and low driver spin rate
US6692380B2 (en) 2001-03-23 2004-02-17 Acushnet Company Golf ball with high density center
US7125345B2 (en) * 2002-10-24 2006-10-24 Acushnet Company Low deformation golf ball
US20050187347A1 (en) * 2001-03-23 2005-08-25 Sullivan Michael J. Golf ball composition having substantially no ZDA coagent
US7131915B2 (en) * 2001-04-10 2006-11-07 Acushnet Company Three-layer-cover golf ball
US7652086B2 (en) * 2001-06-26 2010-01-26 Acushnet Company Highly-neutralized thermoplastic copolymer center for improved multi-layer core golf ball
US9457233B2 (en) 2001-06-26 2016-10-04 Acushnet Company Three-layer-core golf ball having highly-neutralized polymer outer core layer
US8152654B2 (en) 2001-06-26 2012-04-10 Acushnet Company Three-layer-core golf ball having highly-neutralized polymer outer core layer
US20090325731A1 (en) 2001-06-26 2009-12-31 Sullivan Michael J Highly-neutralized thermoplastic copolymer center for improved multi-layer core golf ball
US8025593B2 (en) * 2001-06-26 2011-09-27 Acushnet Company Multi-layer-core golf ball having highly-neutralized polymer outer core layer
US6756436B2 (en) 2001-06-26 2004-06-29 Acushnet Company Golf balls comprising highly-neutralized acid polymers
US6632147B2 (en) * 2001-10-09 2003-10-14 Acushnet Company Golf ball with vapor barrier layer and method of making same
US9339694B2 (en) * 2001-11-28 2016-05-17 Acushnet Company Multi-layer golf ball
US9539470B2 (en) * 2001-11-28 2017-01-10 Acushnet Company Multi-layer golf ball
US7014575B2 (en) * 2001-11-28 2006-03-21 Acushnet Company Golf ball with multi-layered core
US20070270244A1 (en) * 2001-11-28 2007-11-22 Sullivan Michael J Multi-Layer Golf Ball
US7238122B2 (en) * 2002-08-27 2007-07-03 Acushnet Company Ormocer composites for golf ball components
US7037965B2 (en) * 2002-08-27 2006-05-02 Acushnet Company Golf balls comprising glass ionomers, ormocers, or other hybrid organic/inorganic compositions
US20040132552A1 (en) * 2002-09-27 2004-07-08 Chen John Chu Golf balls with soft, resilient bimodal ionomeric covers
US6783468B2 (en) 2002-10-24 2004-08-31 Acushnet Company Low deformation golf ball
US7138460B2 (en) * 2002-10-24 2006-11-21 Acushnet Company Compositions for use in golf balls
US7108921B2 (en) * 2002-10-24 2006-09-19 Acushnet Company Compositions for use in golf balls
US7132480B2 (en) * 2002-10-24 2006-11-07 Acushnet Company Compositions for use in golf balls
US7163471B2 (en) * 2003-01-10 2007-01-16 Taylor Made Golf Company, Inc. Golf balls having sound-altered layers and methods for making them
US7144958B2 (en) 2003-05-21 2006-12-05 E. I. Du Pont De Nemours And Company Articles prepared from compositions modified with organic fiber micropulp
US7654918B2 (en) * 2004-01-12 2010-02-02 Acushnet Company Multi-layer core golf ball having thermoset rubber cover
US7193000B2 (en) * 2004-05-15 2007-03-20 Acushnet Company Compositions for use in golf balls
US7199192B2 (en) * 2004-12-21 2007-04-03 Callaway Golf Company Golf ball
US7819761B2 (en) 2005-01-26 2010-10-26 Taylor Made Golf Company, Inc. Golf ball having cross-core hardness differential and method for making it
US8177665B2 (en) 2005-02-01 2012-05-15 Taylor Made Golf Company, Inc. Multi-layer golf ball
US20070035063A1 (en) * 2005-08-10 2007-02-15 Lavallee Gerald A Two-stage reaction injection molded golf ball
US7524251B2 (en) * 2005-08-30 2009-04-28 Callaway Golf Company Golf products produced by a stoichiometrically imbalanced RIM system
US20070135235A1 (en) * 2005-10-13 2007-06-14 Kennedy Thomas J Iii Fast-Chemical-Reaction-Produced Golf Product Comprising a Caprolactam Polyol
US8030411B2 (en) 2005-12-21 2011-10-04 Taylor Made Golf Company, Inc. Polymer compositions comprising peptizers, sports equipment comprising such compositions, and method for their manufacture
US20070270242A1 (en) * 2006-05-17 2007-11-22 Callaway Golf Company Polybutadiene diols for unique polyurethane
JP5602337B2 (ja) * 2006-07-24 2014-10-08 アクシュネット カンパニー 改良された多層コアゴルフボール用の高度に中和された熱可塑性コポリマーのセンタ
US8088026B2 (en) * 2006-10-03 2012-01-03 E. I. Du Pont De Nemours And Company Phase transition golf ball and method of use
US8211976B2 (en) 2007-12-21 2012-07-03 Taylor Made Golf Company, Inc. Sports equipment compositions comprising a polyurethane, polyurea or prepolymer thereof and a polyfunctional modifier
US8096899B2 (en) 2007-12-28 2012-01-17 Taylor Made Golf Company, Inc. Golf ball comprising isocyanate-modified composition
US9643060B2 (en) 2008-01-10 2017-05-09 Acushnet Company Multi-layer core golf ball
US9823090B2 (en) 2014-10-31 2017-11-21 Allegro Microsystems, Llc Magnetic field sensor for sensing a movement of a target object
US10226670B2 (en) 2008-01-10 2019-03-12 Acushnet Company Multi-layer core golf ball
US9649538B2 (en) 2013-08-05 2017-05-16 Acushnet Company Multi-layer core golf ball
US9717957B2 (en) 2013-08-05 2017-08-01 Acushnet Company Multi-layer core golf ball
US9943730B2 (en) 2008-01-10 2018-04-17 Acushnet Company Multi-layer core golf ball
US9662542B2 (en) 2008-01-10 2017-05-30 Acushnet Company Multi-layer core golf ball
US8500574B2 (en) 2009-06-29 2013-08-06 Acushnet Company Multi-layer golf ball
US8575278B2 (en) 2009-12-31 2013-11-05 Taylor Made Golf Company, Inc. Ionomer compositions for golf balls
US8674023B2 (en) 2009-12-31 2014-03-18 Taylor Made Golf Company, Inc. Ionomer compositions for golf balls
US8629228B2 (en) 2009-12-31 2014-01-14 Taylor Made Golf Company, Inc. Ionomer compositions for golf balls
US9592425B2 (en) 2012-04-20 2017-03-14 Acushnet Company Multi-layer core golf ball
US9649539B2 (en) 2012-04-20 2017-05-16 Acushnet Company Multi-layer core golf ball
US9643061B2 (en) 2013-08-05 2017-05-09 Acushnet Company Multi-layer core golf ball
US9737764B2 (en) 2013-08-05 2017-08-22 Acushnet Company Multi-layer core golf ball
TWI647267B (zh) * 2017-04-14 2019-01-11 宇榮高爾夫科技股份有限公司 殼體具有網狀結構的高爾夫球的製造方法
US11185741B1 (en) * 2020-05-27 2021-11-30 Callaway Golf Company Method and system for utilizing radio-opaque fillers in multiple layers of golf balls
US11642571B2 (en) * 2020-05-27 2023-05-09 Topgolf Callaway Brands Corp. Method and system for utilizing radio-opaque fillers in multiple layers of golf balls
US11318354B2 (en) * 2020-05-27 2022-05-03 Callaway Golf Company Method and system for utilizing radio-opaque fillers in multiple layers of golf balls

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5439227A (en) * 1992-08-31 1995-08-08 Bridgestone Sports Co., Ltd. Multi-piece solid golf ball

Family Cites Families (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US696353A (en) * 1901-12-14 1902-03-25 Kempshall Mfg Co Golf-ball.
US696366A (en) * 1901-12-18 1902-03-25 Kempshall Mfg Co Golf-ball.
FR82838E (fr) * 1962-12-27 1964-04-24 Centre Nat Rech Scient Dispositif pour l'abaissement de la température d'un corps par son propre rayonnement et application à la production de froid
US3359231A (en) * 1965-02-06 1967-12-19 Polymer Corp Synthetic trans-1, 4-polymers of conjugated diolefins with improved hardening rate properties
US3490146A (en) * 1967-11-09 1970-01-20 Niles F Guichet Pantograph
US4123061A (en) * 1976-05-20 1978-10-31 Acushnet Company Ball and process and composition of matter for production thereof
FR2418250A1 (fr) * 1978-02-24 1979-09-21 Ato Chimie Enveloppe en matiere polymere thermoplastique pour balles de golf et balles de golf comportant une telle enveloppe
JPS5683367A (en) * 1979-12-10 1981-07-07 Bridgestone Tire Co Ltd Golf ball
JPS5734874A (en) * 1980-08-13 1982-02-25 Bridgestone Tire Co Ltd Golf ball
US4431193A (en) * 1981-08-25 1984-02-14 Questor Corporation Golf ball and method of making same
JPS59194760A (ja) * 1983-04-21 1984-11-05 住友ゴム工業株式会社 スリ−ピ−スソリツドゴルフボ−ル
JPS6014877A (ja) * 1983-07-06 1985-01-25 住友ゴム工業株式会社 ソリッドゴルフボール
JPS62137075A (ja) * 1984-10-30 1987-06-19 住友ゴム工業株式会社 マルチピ−スソリツドゴルフボ−ル
US4650193A (en) * 1984-12-10 1987-03-17 Spalding & Evenflo Companies, Inc. Golf ball
JPS62181069A (ja) * 1986-02-04 1987-08-08 キャスコ株式会社 ソリツドスリ−ピ−スゴルフボ−ル
JPH078301B2 (ja) * 1986-05-23 1995-02-01 ブリヂストンスポーツ株式会社 ソリツドゴルフボ−ル
US5159035A (en) * 1986-06-10 1992-10-27 The Dow Chemical Company Homogenous copolymerization of non-polar monomers with ionic amphiphilic monomers
US4848770A (en) * 1986-10-20 1989-07-18 Wilson Sporting Goods Co. Three-piece solid golf ball
US4884814A (en) * 1988-01-15 1989-12-05 Spalding & Evenflo Companies, Inc. Golf ball
JPH02107275A (ja) * 1988-10-17 1990-04-19 Sumitomo Rubber Ind Ltd ゴルフボール
JP3124533B2 (ja) * 1989-02-06 2001-01-15 住友ゴム工業株式会社 ゴルフボール
JP2674627B2 (ja) * 1989-03-01 1997-11-12 住友ゴム工業株式会社 ラージサイズのスリーピースソリッドゴルフボール
US5150906A (en) * 1989-03-10 1992-09-29 Lisco, Inc. Multi-piece golf balls and methods of manufacture
JP2680405B2 (ja) * 1989-04-04 1997-11-19 住友ゴム工業株式会社 ラージサイズのスリーピースソリッドゴルフボール
US5000459A (en) * 1989-07-05 1991-03-19 Acushnet Company Golf ball cover
US4986545A (en) * 1989-12-13 1991-01-22 Spalding Sports Worldwide Golf ball compositions
KR920006255B1 (ko) * 1990-06-01 1992-08-01 일야실업 주식회사 세겹으로 이루어진 골프공
US5120791A (en) * 1990-07-27 1992-06-09 Lisco, Inc. Golf ball cover compositions
JP2915108B2 (ja) * 1990-08-10 1999-07-05 住友ゴム工業株式会社 ゴルフボール
FR2666018A1 (fr) * 1990-08-22 1992-02-28 Salomon Sa Balle de golf.
US5026067A (en) * 1990-11-08 1991-06-25 Gentiluomo Joseph A Golf ball
US5492972A (en) * 1990-12-10 1996-02-20 Acushnet Company Golf ball cover
US5104126A (en) * 1991-07-08 1992-04-14 Gentiluomo Joseph A Golf ball
US5314187A (en) * 1991-07-26 1994-05-24 Wilson Sporting Goods Co. Golf ball with improved cover
US5368304A (en) * 1993-04-28 1994-11-29 Lisco, Inc. Low spin golf ball
CA2078842C (fr) * 1991-10-15 2000-03-07 Michael J. Sullivan Enveloppes de balle de golf contenant des ionomeres tres acides
JP3391450B2 (ja) * 1992-01-31 2003-03-31 イー・アイ・デュポン・ドゥ・ヌムール・アンド・カンパニー ゴルフボールの表皮用の高弾性イオノマー組成物
CA2088140C (fr) * 1992-06-19 2000-08-22 Michael J. Sullivan Ionomeres tres acides et compositions de recouvrement de balle de golf les comportant
JP3564641B2 (ja) * 1993-06-01 2004-09-15 ザ、トップ・フライト、ゴルフ、カムパニ 改良された多重層ゴルフボール
JP2658811B2 (ja) * 1993-07-08 1997-09-30 ブリヂストンスポーツ株式会社 スリーピースソリッドゴルフボール
JP2910516B2 (ja) * 1993-07-08 1999-06-23 ブリヂストンスポーツ株式会社 スリーピースソリッドゴルフボール
US5609532A (en) * 1993-07-08 1997-03-11 Bridgestone Sports Co., Ltd. Thread-wound golf ball
US5415937A (en) * 1993-10-21 1995-05-16 Dunlop Slazenger Corporation Golf ball cover
JP3080290B2 (ja) * 1993-11-02 2000-08-21 住友ゴム工業株式会社 ゴルフボール
JPH09164224A (ja) * 1995-10-11 1997-06-24 Sumitomo Rubber Ind Ltd ソリッドゴルフボール

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5439227A (en) * 1992-08-31 1995-08-08 Bridgestone Sports Co., Ltd. Multi-piece solid golf ball

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1096977A1 (fr) * 1998-07-10 2001-05-09 Dunlop Sports Group Americas Inc. Balle de golf longue distance de type deux pieces
EP1096977A4 (fr) * 1998-07-10 2006-03-22 Taylor Made Golf Co Balle de golf longue distance de type deux pieces
GB2362580B (en) * 1999-02-11 2003-12-10 Spalding Sports Worldwide Inc Low spin golf ball utilizing perimeter weighting
JP2003502123A (ja) * 1999-06-17 2003-01-21 スポルディング、スポーツ、ワールドワイド、インク 多層カバーを伴うゴルフボール
WO2014193777A1 (fr) * 2013-05-31 2014-12-04 Nike Innovate C.V. Balle de golf multicouche thermoplastique
US9272189B2 (en) 2013-05-31 2016-03-01 Nike, Inc. Thermoplastic multi-layer golf ball

Also Published As

Publication number Publication date
GB2333715A (en) 1999-08-04
JP2000505679A (ja) 2000-05-16
AU5246098A (en) 1998-05-29
JP3607301B2 (ja) 2005-01-05
US5810678A (en) 1998-09-22
GB9910473D0 (en) 1999-07-07
GB2333715B (en) 2000-12-20

Similar Documents

Publication Publication Date Title
US5810678A (en) Multilayer golf ball
US5813923A (en) Golf ball
US5947842A (en) Multi-layer low-spin golf ball
US5965669A (en) Multi-layer golf ball and composition
US6315680B1 (en) Multilayer golf ball
US6124389A (en) Multilayer golf ball and composition
US5759676A (en) Multilayer golf ball
US5688191A (en) Multilayer golf ball
US6634962B2 (en) Crosslinked foam as filler in an inner layer or core of a multi-component golf ball
US6503156B1 (en) Golf ball having multi-layer cover with unique outer cover characteristics
US6302808B1 (en) Method of making a golf ball with a multi-layer core
US6780933B2 (en) Multi-layered golf ball and composition
US20010031671A1 (en) Multi layer golf ball
WO2001023045A1 (fr) Balle de golf multicouche et composition
US5962140A (en) Golf ball comprising fluoropolymer
CA2373671A1 (fr) Balle de golf multicouches a distance
US7255657B2 (en) Golf ball composition
WO1999042184A1 (fr) Composition de balle de golf
US6114455A (en) Golf ball composition comprising high acid and VLMI ionomers
US6458892B1 (en) Multilayer golf ball and composition
JP2000504253A (ja) ゴルフボール組成物
US20020032078A1 (en) Method of making a golf ball with a multi-layer core
US20010039219A1 (en) Golf ball having multi-layer cover with unique inner cover characteristics
GB2367250A (en) Golf ball including foamed particles or granules

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA GB JP NZ

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref country code: GB

Ref document number: 9910473

Kind code of ref document: A

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA